Preparation Of Porous Chitosan Supported Metal Tetrakis [4-(Sodium-Sulfonato) Phenyl]Porphyrin And Research Of Performance

Metaloporphyrins acted as an artificial model of cytochrome P-450enzyme, can efficiently catalyze aerobic oxidation of hydrocarbon to corresponding oxygeneous coMPaounds under mild reaction conditions. However, there are two shortcomings for metal porphyrins, one is easily to be oxidized to dimer and lose their catalytic activity, and another is difficult to recover them in homogeneous catalysis process. Therefore, exploration of suitable supports for metal porphyrin has become a challenge subject. In this thesis, metal tetrakis [4-(sodium-sulfonato)phenyl]porphyrins were prepared by coordination of porous/iMPaerforated chitosan to metal ion center of porphyrins and dipole-dipole interaction of metaloporphyrin with porous/imp aerforated chitosan. Structure of supported catalysts was characterized by spectroscopic techniques, including UV-Vis, TG, FT-IR and so on. Catalysis of two type supported metaloporphyrins and unsupported catalyst for oxygen oxidation of toluene is investigated, and then their catalytic performances were compared with each other. Catalytic performance for the porous chitosan-supported metaloporphyrin materials are summed up and related catalytic mechanism was suggested.The main content is as following: 1.Current advance of research for metaloporphyrins and supported metaloporphyrins, and chemical and engineering technology for toluene oxidation to benzaldehyde and phemethylol is briefly introduced.2.Metaloporphyrins were synthesized using literature methods and corresponding porous/iMPaerforated chitosan-supported metal porphyrins [M TPPS/p-/imp-CTS] were prepared by self-designed methods described in this text.3.Chitosan supported metaloporphyrins were characterized by Ultraviolet-visible (UV-Vis) and Fourier transform infrared (FT-IR) spectroscopies, Thermogravimetric analysis (TG) and Microscopic technique and so on, for confirming a key linkage between metaloporphyrin and chitosan and the physicochemical properties of supported catalysts.4. Catalysis of supported catalysts, M TPPS/p-/imp-CTS for oxidation of toluene to corresponding aldehyde (ald.) and alcohol (alc.) were investigated in absence of any additional solvents and reductants. Effects of various factors, such as reaction tempaerature, oxygen pressure, reaction time and amount of metaloporphyrin on toluene oxidation were analyzed and discussed. Under the appropriate reaction conditions, experimental results for toluene oxidation over tow type chitosan-supported M-TPPS and unsupported metaloporphyrins respectively are compared each other. It shows that yields (ald.+alc.) obtained from the toluene oxidation over M(Mn, Co and Fe) TPPS/p-CTS are1.2,1.4and1.6times bigger than M(Mn, Co and Fe) TPPS/imp-CTS and1.5,1.2and1.6 times bigger than M(Mn, Co and Fe) TPPS, respectively.5.Based on our experiment data and our best understanding to the relevant catalysis mechanism of supported metaloporphyrins for hydrocarbon oxidation reported in previous literatures, it is suggested that catalysis mechanism of MTPPS/CTS for oxygen oxidation of toluene is a ridical reaction process.